-1
ν, cm ): 1751 (C O), 1648, 1490 (Ar).
1
H NMR spectrum (CDCl , δ, ppm, J/Hz): 7.42~7.22 (m, 30H, Ar-H), 5.85 (dd, 1H, J = 3.78, H-1), 5.77 (dd, 1H,
3
1,2
J1'’,2 = 4.09, H-1 ), 5.45 (m, 1H, H-3 ), 5.39 (m, 1H, H-4 ), 5.36 (dd, 1H, J3,4 = 9.46, H-3), 5.20 (dd, 1H, J4,5 = 8.29, H-4), 4.96
dd, 1H, J4 -5 = 4.49, H-4 ), 4.92 (dd, 1H, J2 ,3 = 4.25, H-2 ), 4.85 (dd, 1H, J2,3 = 7.98, H-2), 4.49 (dd, 1H, J3',4' = 5.91, H-3 ),
.33 (dd, 1H, J5,6a = 2.0, J5,6b = 4.60, H-5), 4.30 (m, 1H, H-6b ), 4.28 (m, 1H, H-5 ), 4.16 (dd, 1H, J6a,6b = 8.03, H-6b), 4.02
m, 1H, H-6a ), 4.00 (m, 1H, H-5 ), 3.95 (dd, 1H, J6a,6b = 8.03, H-6a), 3.83 (m, 1H, H-6b ), 3.73 (m, 1H, H-6a ), 3.30 (dd, 1H,
J1a',1b' = 8.04, H-1b ), 3.13 (dd, 1H, J = 8.04, H-1a ), 2.15~1.90 (27H, 9CH CO).
(
4
(
1a',1b'
3
13
C NMR spectrum: 170.9, 170.6, 170.4, 170.3, 170.1, 169.7, 169.5, 169.3, 169.1 (C O), 143.6, 129.8, 129.1, 128.9,
1
7
28.7, 128.2, 127.9, 127.7, 127.5, 127.1 (Ar-C), 101.8 (C-2 ), 97.5 (C-1 ), 92.8 (C-1), 88.4 (C-3 ), 87.4 (C-5 ), 76.6 (C-4 ),
5.4 (C-2 ), 74.1 (C-2), 73.9 (C-3 ), 73.5 (C-3), 73.4 (C-4 ), 72.6 (C-4), 72.3 (C-5 ), 71.8 (C-5), 70.2 (C-6 ), 64.1 (C-1 ), 63.4
(
C-6 ), 62.4 (C-6), 20.7 (CH CO).
3
+
Mass spectrum (FAB), m/z (I , %): 1366 [M ] (7), 1019 (7), 242 (100).
Compound 3. Colorless syrup, 3.1 g (26.8%), R 0.28 (A), 0.17 (B), [α] +22.6 (c 1, CHCl ). Found (%): C 58.38,
rel
2
5
o
f
D
3
-1
H 5.69. C H O . Calc. (%): C 58.64, H 5.70. IR spectrum (KBr, ν, cm ): 1754 (C O), 1493 (Ar).
57 66 26
1
H NMR (CDCl , δ, ppm, J/Hz): 7.43~7.22 (m, 15H, Ar-H), 5.84 (dd, 1H, J1,2 = 3.93, H-1), 5.79 (dd, 1H, J1 ,2 = 3.76,
3
H-1 ), 5.58 (m, 1H, H-4 ), 5.38 (m, 1H, H-3), 5.34 (m, 1H, H-3 ), 5.19 (m, 1H, H-4 ), 5.16 (m, 1H, H-4), 4.96 (t, 1H,
J2 ,3 = 4.56, H-2 ), 4.92 (t, 1H, J2,3 = 3.96, H-2), 4.49 (dd, 1H, J3',4' = 6.81, H-3 ), 4.37 (m, 2H, H-5, H-5 ), 4.29 (m, 2H, H-6b,
H-6b ), 4.09 (m, 1H, H-5 ), 3.99 (m, 1H, H-6b ), 3.95 (m, 2H, H-6a, H-6a ), 3.75 (m, 1H, H-6a ), 3.55 (dd, 1H, J1a',1b' = 7.72,
H-1b ), 3.34 (dd, 1H, J
= 7.72, H-1a ), 2.13~1.92 (30H, 10CH CO).
1
a',1b'
3
13
C NMR: 170.7, 170.5, 170.3, 169.9, 169.6, 169.4, 169.2 (C O), 143.8, 129.9, 129.3, 128.9, 128.6, 128.4, 127.9,
127.7, 127.6, 127.3 (Ar-C), 101.7 (C-2 ), 97.6 (C-1 ), 92.9 (C-1), 88.4 (C-3 ), 87.5 (C-5 ), 76.7 (C-4 ), 75.6 (C-2 ), 74.2 (C-2),
7
3.9 (C-3 ), 73.7 (C-3), 73.5 (C-4 ), 72.8 (C-4), 72.6 (C-5 ), 71.9 (C-5), 70.1 (C-6 ), 64.1 (C-1 ), 62.9 (C-6 ), 61.3 (C-6), 20.6
+
(CH CO). Mass spectrum (FAB), m/z (I , %): 1166 [M ] (9), 1090 [M - C H ] (35), 819 (7), 471 (7), 331 (100).
3
rel
6 5
6-O-Triphenylmethyl-2,3,4,1 ,4 ,6 ,2 ,3 ,4 ,6 -deca-O-acetylmelezitose (4) and 6,6 ,6 -Tri-O-triphenylmethyl-
2
,3,4,1 ,4 ,2 ,3 ,4 -octa-O-acetylmelezitose (5). Compounds 2, 3, 4 and 5 were prepared analogously from anhydrous
melezitose (5 g, 10 mmole) and TrCl (13 g, 44 mmole).
Compound 4. Colorless syrup, 1.9 g (16.4%), R 0.27 (A), 0.16 (B). Found (%): C 58.47, H 5.57. C H O . Calc.
f
57 66 26
-1
(
%): C 58.64, H 5.70. IR spectrum (KBr, ν, cm ): 1753 (C O), 1498 (Ar).
1
H NMR (CDCl , δ, ppm, J/Hz): 7.40-7.25 (m, 15H, Ar-H), 5.80 (dd, 1H, J1,2 = 3.89, H-1), 5.78 (dd, 1H, J1 ,2 = 3.76,
3
H-1 ), 5.56 (dd, 1H, J4',5' = 7.21, H-4 ), 5.35 (dd, 1H, J3,4 = 9.18, H-3), 5.31 (m, 1H, H-3 ), 5.15 (dd, 1H, J3 ,4 = 3.57, H-4 ),
.12 (dd, 1H, J3,4 = J4,5 = 9.18, H-4), 4.95 (dd, 1H, J2 ,3 = 3.24, H-2 ), 4.91 (dd, 1H, J2,3 = 3.78, H-2), 4.49 (dd, 1H, J3',4' = 6.78,
H-3 ), 4.38 (m, 1H, H-5 ), 4.29 (m, 1H, H-5 ), 4.27 (m, 1H, H-6b ), 4.24 (m, 1H, H-5), 4.17 (m, 1H, H-6b ), 4.00 (m, 1H, H-
a ), 3.97 (m, 1H, H-6a ), 3.77 (m, 1H, H-6b), 3.65 (m, 1H, H-6a), 3.57 (dd, 1H, J1a',1b' = 8.04, H-1b ), 3.33 (dd, 1H,
J1a'-1b' = 8.04, H-1a ), 2.15-1.97 (30H, 10CH CO).
5
6
3
13
C NMR: 170.6, 170.4, 170.2, 169.8, 169.6, 169.3, 169.1 (C O), 143.8, 129.9, 129.3, 128.9, 128.7, 128.5, 127.9,
1
7
27.8, 127.5, 127.2 (Ar-C), 102.3 (C-2 ), 98.1 (C-1 ), 92.9 (C-1), 88.1 (C-3 ), 87.3 (C-5 ), 76.6 (C-4 ), 75.4 (C-2 ), 74.1 (C-2),
3.8 (C-3 ), 73.6 (C-3), 73.3 (C-4 ), 72.6 (C-4), 72.4 (C-5 ), 71.8 (C-5), 70.1 (C-6 ), 64.3 (C-1 ), 62.8 (C-6 ), 62.5 (C-6), 20.8
(
CH CO).
3
+
+
Mass spectrum (FAB), m/z (I , %): 1166 [M] (10), 1090 [M - C H ] (30), 531 (16), 331 (100).
Compound 5. Colorless syrup, 5.3 g (34.2%), R 0.65 (A), [α] +91.3 (c 0.1, CHCl ). Found (%): C 70.50, H 6.02.
rel
6 5
2
5
o
f
D
3
-1
C H O . Calc. (%): C 69.72, H 5.79. IR spectrum (KBr, ν, cm ): 1745 (C O), 1600, 1490 (Ar).
9
1
90 24
1
H NMR (CDCl , δ, ppm, J/Hz): 7.43~7.20 (m, 45H, Ar-H), 5.66 (dd, 1H, J1,2 = 3.67, H-1), 5.65 (dd, 1H, J1 ,2 = 3.62,
3
H-1 ), 5.41 (dd, 1H, J3',4' = 5.94, H-3 ), 5.38 (m, 2H, H-3, H-3 ), 4.99 (m, 2H, H-4, H-4 ), 4.86 (m, 2H, H-2, H-2 ), 4.51 (dd,
1
H, J4 ,5 = 6.34, H-4 ), 4.29 (m, 2H, H-5, H-5 ), 4.01 (m, 1H, H-6b ), 3.86 (m, 4H, H-6, H-6 ), 3.82 (m, 1H, H-5 ), 3.74 (m,
H, H-6a ), 3.32 (dd, 1H, J = 8.04, H-1b ), 3.15 (dd, 1H, J1a',1b' = 8.04, H-1a ), 2.15~1.90 (24H, 8CH CO).
1
1
a',1b'
3
13
C NMR: 171.1, 170.9, 170.6, 170.3, 170.2, 169.8, 169.6, 169.2, 168.9 (C O), 143.7, 129.9, 129.2, 128.9, 128.8,
1
2
6
28.3, 127.9, 127.7, 127.3, 126.7 (Ar-C), 101.9 (C-2 ), 95.6 (C-1 ), 92.8 (C-1), 89.0 (C-3 ), 87.1 (C-5 ), 76.4 (C-4 ), 75.3 (C-
), 74.1 (C-2), 73.8 (C-3 ), 73.5 (C-3), 73.3 (C-4 ), 72.4 (C-4), 72.1 (C-5 ), 71.5 (C-5), 70.1 (C-1 ), 63.4 (C-6 ), 63.0 (C-6 ),
2.2 (C-6), 20.7 (CH CO).
3
2
,3,4,1 ,4 ,2 ,3 ,4 ,6 -Nona-O-acetylmelezitose (6). Compound 2 (4.5 g, 3.3 mmole) was dissolved in CH Cl
2 2
399